Shortest multiple disconnected path for the analysis of entanglements in two- and three-dimensional polymeric systems

Abstract

We present an algorithm which returns a shortest path and related number of entanglements for a given configuration of a polymeric system in 2 or 3 dimensions. Rubinstein and Helfand, and later Everaers et al. introduced a concept to extract primitive paths for dense polymeric melts made of linear chains (a multiple disconnected multibead 'path'), where each primitive path is defined as a path connecting the (space-fixed) ends of a polymer under the constraint of non-interpenetration (excluded volume) between primitive paths of different chains, such that the multiple disconnected path fulfills a minimization criterion. The present algorithm uses geometrical operations and provides a-model independent-efficient approximate solution to this challenging problem. Primitive paths are treated as 'infinitely' thin (we further allow for finite thickness to model excluded volume), and tensionless lines rather than multibead chains, excluded volume is taken into account without a force law. The present implementation allows to construct a shortest multiple disconnected path (SP) for 2D systems (polymeric chain within spherical obstacles) and an optimal SP for 3D systems (collection of polymeric chains). The number of entanglements is then simply obtained from the SP as either the number of interior kinks, or from the average length of a line segment. Further, information about structure and potentially also the dynamics of entanglements is immediately available from the SP. We apply the method to study the 'concentration' dependence of the degree of entanglement in phantom chain systems.